TW201237110A - Disperse azo dyes - Google Patents

Abstract

The present invention relates to disperse azo dyes based on diazo components having at least one fluorine-containing substituent and an 2, 6-diaminosubstituted pyridine coupling component, to a process for the preparation of such dyes and to their use in the dyeing or printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials.

Description

201237110 VI. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for dispersing dyed dyes based on a heavy-weight component having at least one fluorine-containing substituent and its semi-synthesis and especially hydrophobicity. The use of fibrous materials is more particularly useful in the dyeing or printing of textile materials. [Prior Art] A dispersed azo dye having an aniline diazo component and a 2,6-diamino group-substituted H-coupling component has long been known and used for dyeing of hydrophobic fibrous materials. However, it has been found that dyeing or printing using currently known dyes does not in all cases meet the current requirements of the automotive industry, particularly with respect to its light fastness, in particular its thermal fastness to light. It has now surprisingly been found that the dyes of the present invention largely conform to the above criteria. SUMMARY OF THE INVENTION The present invention is therefore directed to achieving dyeing with excellent light fastness and additionally exhibiting good dye-build-up in both exhaustion and hot-melt processes and fabric printing. Disperse dyes. The dye of the present invention corresponds to formula (1)

NHR, (1) 201237110 R2 and: bis: fluorine, tri-I methyl, trifluoromethoxy or tri-lactyl, this independently represents hydrogen, Ci-C丨2 alkyl, Ci-Cl2 alkane Oxygen, cyano, nitro, trifluoromethyl or _C hydrazine substituted or via - or more rp 6 VIII, R6 is a sub-substituted kCd-based alkoxy group, (d), an amine or a pro-forminogen C: 4::5 represents hydrogen or a phenyl group which is unsubstituted or substituted with - or a plurality of Cl_Ci2 alkyl groups, 1 12 oxy or trifluoromethyl group, and the restriction condition is one of A garden R4 and r5. Or h is a group of 俅仵 and the other is unsubstituted or taken, the year " and the restriction is that if RI represents the trifluoro ortho position in the azo group, then R2 and r3 At least - not hydrogen. " When any of the groups R1, R2 or R6 or any of the substituents 114 or R5 is a topographic group, the group or the groups may be a straight or branched chain group. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-glycol Base, n-octyl, isooctyl, n-decyl and n-dodecyl. The substituted alkyl group is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-aminoethyl, 2-aminopropyl, 4-aminobutyl, cyano Methyl, 2, cyanoethyl, 2-oxyethyl, 2-bromoethyl and 4- butyl. Examples of alkoxy groups are decyloxy, ethoxy, ipropoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, tert-butoxy, n-pentyloxy , neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, isooctyloxy, n-decyloxy and n-dodecyloxy. Suitable halogen substituents are fluorine and especially gases and bromine. 4 201237110 In the formula (1), R丨 is preferably a fluorine or a trifluoromethyl group. Also preferred are the dyes of formula (1) wherein R2 and R3 represent hydrogen, fluorine, chlorine, bromine, cyano or triazole. In the formula (1), R4 and R5 preferably represent hydrogen or a phenyl group substituted with a trifluoromethyl group, n-propyl group, n-butyl group or n-butoxy group. Preferably, the dye of the formula (1) represented by the formula (la):

Wherein R is a fluoro or trifluoromethyl group, R2 represents a sulphur, a gas, a desert or a succinct group, R3 represents a hydrogen, > odor, a cyano group or a determinant * and R4 and R5 are as defined above. R4 and R5 in the formula (1a) are preferably hydrogen or phenyl. The invention also relates to a process for the preparation of an azo dye of the formula (1) as defined above, wherein a compound of the formula (2), wherein R!, R 2 and R 3 are as defined above, is diazotized according to customary procedures, followed by Coupling with the coupling component of formula (3),

201237110 wherein the ruler 4 and the ruler 5 are as defined above. The aniline of formula (2) is known or can be prepared according to known methods. Some of the commercially available anilines of formula (2) are, for example, 3-trifluoromethyl-6-methylaniline, 3-difluoroindolyl-4-methylindolamine, 2-chloro-4-tri Fluoromethoxyaniline, 2-Ga-4-difluoromethylaniline, 2-Ga-5-trifluorodecylaniline, 4-Gas-2-trifluoromethylaniline, 4-Chloro-3-Trifluoro Methylaniline, 3,5-bis-(trifluoromethyl)aniline, 3-trifluoromethyl-4-cyanoaniline, 3-trifluoromethyl-4-nitroaniline, 2·bromo_4_ Trifluoromethoxyaniline, 4-bromo-2-trifluoromethoxyaniline, 2-bromo-4-trifluorodecylaniline, 2-bromo-5-trifluoromethylaniline, 4-bromo-2- Trifluorodecylamine, 4-bromo-3-trifluorodecylaniline, 2-fluoro-3-trifluorodecylaniline, 2-fluoro-5-trifluoromethylaniline, 2-fluoro-6-tri Fluoromethylaniline, 4-fluoro-2-trifluoromethylaniline, heart fluoride trifluorodecyl aniline, 2-nitro-4-trifluoromethylaniline, 3-nitro-6-trifluorodecyl aniline , 4-nitro-2-trifluorodecylaniline, 2,4-dinitro-6-trifluorodecylaniline, 2-bromo-4-nitro-6-trifluorodecylaniline and 2-cyano Base 4-nitro-6-trifluoromethylaniline. The coupling component of formula (3) is likewise known or can be obtained by known methods, for example by the method described in U.S. Patent 3,853,895. According to this method, 2,6-dioxa-3-cyano-4-methylpyridine is sequentially reacted with ammonia and optionally substituted aniline. Since the reactivity of the two gas atoms in the educt is different, two isomeric products are usually obtained. For example, in the first step, 2,6-dioxa·3-cyano-4-pyridinyl is reacted with aniline to produce 2-anilino-3-cyano-4-methyl-6-pyridine and Mixture of 2_gas-3-cyano-4-methyl-6-anilinopyridine. 6 201237110 Therefore, the final product obtained by subsequent reaction with ammonia is mainly composed of the same isomer ratio of 2-anilino-3-cyano-4-methyl-6-aminopyridine and 2-amino-3-cyano -4-Methyl-6-anilinopyridine composition. The invention therefore also relates to dye mixtures comprising at least two structurally different azo dyes of the formula (1) of claim 1 of the patent application. The diazotization is carried out in a manner known per se, for example using sodium nitrite in an acidic medium such as hydrochloric acid or sulfuric acid. However, diazotization can also be carried out using other diazotizing agents, for example, using nitrososulfuric acid. Other acids may be present in the reaction medium in the diazotization, such as dish acid, sulfuric acid, acetic acid, propionic acid or hydrochloric acid or a mixture of such acids, such as a mixture of propionic acid and acetic acid. Linearization is preferably carried out at temperatures ranging from -HTC to thief (eg __ to room temperature). 'Dishes' coupling of the diazotized compound with the coupling component of formula (3) is likewise in a known manner, for example in acidity, In aqueous or aqueous organic media, it is preferably carried out at temperatures up to 3 ° C, especially below HTC. Examples of the acid used are hydrochloric acid, acetic acid, propionic acid, sulfuric acid and phosphoric acid. The invention also relates to dye mixtures comprising at least one dye of the formula (1) and at least one dye different from the dye of the formula (1). Suitable dyes suitable for mixing with the dye of the formula (1) of the present invention are, for example, C丄Disperse Yellow 42, CL Disperse Yellow 51, CJ. Disperse Yellow... Disperse Yellow 25 Bu CI Solvent Yellow 163, αι•Disperse Orange 157, ~匕仙Red Ting Bu c!, Disperse ^ Red 55, CL Disperse Red 55:1, c丄 Disperse Red 59, c] Disperse Red 6〇, . 2 Disperse Red 86, 匚丄 Disperse Red 9i, C丄 Disperse Red 仏 to Disperse Red (1) 乂丄 Disperse Red (4) Heart Disperse Red (9) to 201237110 Disperse Red 279, cI Distribution έτ 1 λι ο τ, Moon, 302, C.1. Disperse Red 302:1, CI Disperse Red 380, C.1 ·Disperse red 3 8 jc ι divide province 1 c < u · knife dare red 385, cI · disperse purple 57, ci knife moon blue 27, CI disperse blue 54, C1 T eight au monitor 54 UI. Disperse blue 56, CI Disperse Blue 60, CI Disperse Blue 77 and C.〗 Disperse Blue 379. The dye mixtures of the present invention can be prepared, for example, by simple, individual dyeing. The amount of individual dyes in the dye mixture of the present invention can vary over a wide range. The dye mixture of the invention preferably contains at least 10% by weight, preferably at least

20% by weight and especially at least 4 η tongues. / Λ L Eight masters ^ 4. % by weight - or a plurality of dyes of formula (1). The dyes and dye mixtures of the present invention can be semi-synthesized and especially synthetic, and the fibers (4) are more particularly dyed or printed on textile materials. Contains the same half. The spun material composed of the blend of the hydrophobic fibers (4) and/or the blend of the hydrophobic fibers (4) can also be dyed with the dye or dye mixture of the invention. The semi-synthetic fiber material considered in particular is 2% acetate fiber. And cellulose triacetate. Synthetic hydrophobic fiber materials, especially from linear aromatic polyesters, such as terephthalic acid and glycols (especially ethylene glycol) "polyester, or terephthalic acid with 1,4 · double a condensation product of (a methyl group) ring; a polycarbonate, such as a cardiomethyl-4,4.m form and a phosgene polycarbonate; and a polyethylene-based and polyamide-based fiber Compositions The dyes and dye mixtures of the present invention are applied to fibrous materials according to known dyeing procedures. For example, at 8 (rc to 140. Torr, at 8 201237110 conventional anionic or nonionic dispersing agents and optionally In the presence of a conventional expanding agent (carrier), the polyester fiber material is dyed from the aqueous dispersion by exhaustion. The 21/2 cellulose acetate is preferably dyed at 65. 〇 to 85 〇c and cellulose triacetate. Preferably, it is dyed at 65. (: to a temperature of 11 5 ° C. The dyes and dye mixtures do not dye the wool and cotton which are simultaneously present in the dye bath or make the materials only slightly dyed (excellently dye resistant), so they can also be used satisfactorily for polyester/wool and poly Dyeing of vinegar/cellulosic fiber blend fabrics. The dyes and dye mixtures of the invention are suitable for root dyeing and are suitable for printing. The fiber materials can be in a variety of processing forms, for example in the form of fibers, yarns or non-woven fabrics, in a woven fabric. Or a knitted fabric form. The dyes and dye mixtures of the invention are preferably converted to a dye I stock prior to use. For this purpose, the dyes are ground to have an average particle size of from 〇i to 10 microns. Grinding can be present in the dispersant. For example, the dry powder is ground together or mixed with a dispersing agent to form a paste: 1 true: dried or dried by atomization. The thus obtained preparation is used to prepare a printing paste after adding water. And dye bath. For the decoration, it will use the conventional increase _, such as modified or not r (British gUm), ^ (gumarabic) 'crystalline gum, cowpea powder, tragacanth " methyl Cellulose , by ethyl cellulose, moving powder; or synthetic / residual acrylamide, polyacrylic acid or its copolymer 歹 1 such as poly

4 ACE alcohol D The dyes and dye mixtures of the invention impart the mentioned materials (especially 201237110 polymer materials) for excellent use, such as excellent fastness, such as particularly good light fastness, heat fastness and pleat fastness. , gas fastness and thirst fastness, such as the fastness of the fastness of the financial, the fastness of the sweat and the uniformity of the fastness of the washing; the final dyeing product is also characterized by excellent wear resistance. The good fastness of the resulting dyed product relative to light, especially hot light, should be specifically mentioned. The dyes and dye mixtures of the present invention are also satisfactory for the preparation of mixed chromaticity and other dyes. α The dyes and dye mixtures of the invention are also very suitable for dyeing hydrophobic fibrous materials from supercritical. 2 The present invention also relates to the above-mentioned uses of the dyes and dye mixtures of the invention 'and to semi-synthetic or synthetic hydrophobic fibers # ( In particular, a textile material) method of dyeing or printing wherein the dye of the invention is applied to or incorporated into such materials. Hydrophobic fiber materials such as stomach are preferred. Other matrices which may be treated by the method of the present invention, as well as preferred materials, can be found in the detailed description above regarding the use of the dyes of the present invention. The invention also relates to hydrophobic fibrous materials, especially polyester textile materials, which are dyed or printed by the method. The dyes of the invention are also suitable for modern replication processes, such as thermal transfer printing. [Embodiment] The following examples are intended to illustrate the invention. In the examples, unless otherwise indicated, 'other parts are parts by weight and percentages are by weight. The temperature is given in degrees Celsius. The relationship between the parts by weight and the parts by volume is the same as the relationship between the grams and the centimeters. 201237110 i. Preparation Examples Example Il A · Diazotization 10.67 g of 1 quinone nitrososulfuric acid was placed in a laboratory reaction apparatus. At 15-20 ° C, 3.2 g of 2,4-dibromo- was introduced. 6-Trifluorodecyl phenylamine. After stirring at 1 5 - 20 °C for 2 hours, the mixture was poured into 8 g of ice-water and further mixed for 10 minutes. Excess nitrite is removed by the addition of an aminosulfonic acid. 2.3 g of 2-anilino-3-cyano-4-methyl-6-amino group in 40 ml of 80% acetic acid. ratio. The mixture was prepared in a laboratory reaction apparatus with a mixture of 2-amino-3-cyano-4-methyl-6-phenylamino η and 2 drops of Surfynol 1〇4 E (2,4) were added thereto. 7,7-tetramethyl-5-decyne-4,7·diol After adding 30 g of ice, the diazonium salt solution prepared according to A was slowly added dropwise so that the internal temperature was < 15 C. The mixture was mixed for 1 hour while maintaining the temperature at <15 ° C by adding ice and adjusting the pH to 3 Torr to 3 5 by adding 30% NaOH. After heating to 50 ° C, the mixture was stirred for 30 minutes and The solid was then filtered off with suction, washed with deionized water and dried to give 4.8 g ( 8.0 mmol, 86% yield) of a mixture of formula (101a) and (l lb) of a golden yellow dye.

11 201237110

(101b) λ·= 407 nm Example 1.2 A·Diazotization Your main / dish f 3.2 g of 2-chloro-5-trifluorodecyl phenylamine was dissolved in 20 g of 5 0 / sulphur. Add 〇.丨g ice and 5.5 5 g 1 μ sub-wall sulphuric acid. After stirring at 15-20 ° C for 5 hours, the mixture was poured into 65 ml of acetic acid and stirred for an additional 1 minute. Excess nitrite was removed by the addition of 〇·5 g of aminosulfonic acid. B. Coupling at 5 ° C, 3.58 g of 2-anilino-3-cyano-4-indolyl-6-aminopyridine and 2-amino-3-cyano-4-methyl-6- A mixture of anilinopyridines was added to 0.5 g Surfynol 1〇4 E (2,4,7,9-tetramethyl-5-decyne-4,7-diol) and 0.5 g Baykanol® (dispersant, by Lanxess) Supply) in 65 ml of 80% acetic acid solution. The diazonium salt solution prepared according to A was slowly added dropwise under cooling so that the internal temperature was 0-5t. Subsequently, the mixture was stirred until the internal temperature was about room temperature and then the solid was filtered off by suction, washed with deionized water and dried. A mixture of 6.1 g (yield) of a dye of the formula (1〇2&) and (10 2 b ) was obtained. 12 201237110

(102a) ληι&χ = 458 nm

The dyes listed in Table 1 were prepared in a manner similar to that described in Example 1.1 (102) - (106)°

(103a)

Xmax = 498 nm

13 201237110

(104b) λ· = 440 nm

(105b) (106a)

Xmax = 460 nm n-〇4Hg

Xmax == 502 nm 14 201237110

=486 nm

426 nm 45 8 nm

485 nm

480 nm 15 201237110

16 201237110

(111b) Ren Teng = 441 nm

(113b)

Xmax = 456 nm

17 201237110

(115a) λ max 437 nm

(115b) O-n-C4H9 ^max = 430 nm

(116a) 〇-n-C4H9 χ 5 15 nm

(116b) 〇~n-C4H9

Xmax = 504 nm

(117a) lmax == 545 nm 18 201237110

(117b) into max — 5 3 2 Πm

(118a)

(118b)

(119b)

Xmax = 413 nm 19 201237110

F

(120a) lmax = 430 nm

20 201237110 o2n

(122a) ^max =496 nm

=482 nm

=488 nm

=480 nm

416 nm 21 201237110

F

(124b) n-C4H9

404 nm

= 416 nm

Br

404 nm 428 nm 22 201237110

Br

(126b) n-C4H9 λπΐ3χ = 412 nm

(127a) n-C4H9

Xmax = 432 nm

(127b) n-C4H9

Xmax = 426 nm

23 201237110

(129a) λ· := 448 nm

(130a) n-C4H9 λπι&χ = 462 nm

24 201237110

(131b) λ· = 414 nm

(132b) λτηαχ = 4 12 nm (133a) n-c4H9 λπι&χ = 446 nm 25 201237110

II. Application Examples Example II.1: A polyester fabric sample was prepared in a dye bath containing one of 1% dyes (101)-(1 05) at 135 ° C in a high temperature exhaust dyeing process. dyeing. The resulting dyed product exhibited a value of 26 with respect to light fastness. [Simple description of the diagram] None [Key component symbol description] Benefit 26

Claims (1)

201237110 VII. Patent application scope: 1 A dye of formula (1) 八中 R丨 is fluorine, trifluoromethyl, tri-I and h are each independently oxy or trifluoromethyl, alkoxy, dentate, aryl, germination, :=C:Cl2 stimuli, CA is a cvcd group which is unsubstituted or substituted by one or more c-COOR6', wherein the atom, the amide group, the amine group or the oxime and I represent hydrogen or unsubstituted or one or more a phenyl group, a C 丨 4 丨 1 alkoxy group or a trifluoromethyl group substituted phenyl group, one of which is that one of the group core and the ruler 2 is hydrogen and the other is unsubstituted or A substituted phenyl group, and the restriction is that if Ri represents a trifluoromethyl group ortho to the azo group, at least one of R1 and R3 is not hydrogen. 27 1. A dye according to the formula (1) of claim 1 wherein R is a fluorine or a trifluoromethyl group. 2 A dye according to the formula (1) of claim 1 which is a dye of the formula (1 a ) 3 , such as the formula (1) of claim 1 or 2, wherein R 1 and R 3 represent hydrogen , fluorine, chlorine, bromine, cyano or nitro. 201237110 means Wherein R! is a fluorine or a trifluoromethyl group, and R>2 represents fluorine, chlorine, molybdenum or Schottky's R_3, such as hydrogen, > odor, cyano or argyryl, and R4 and R5 are as claimed in claim 1 Defined by item. 6. A dye according to the formula (1 a) of claim 5, wherein R4 and R5 are hydrogen or phenyl. 7. A method for preparing an azo dye according to the formula (1) of claim 1, wherein the compound of the formula (2) is Rr^^-NH2 (2) wherein Ri, R2 and R3 are as claimed in the patent application As defined in 1 item, diazotized according to the conventional procedure, and then coupled with the coupling component of formula (3), R5hn where R4 and R5 are as defined in item 1 of the scope of the patent application. 8. A dye mixture comprising at least two structurally different azo dyes of the formula (1) of claim 1 of the patent application. 28 201237110 The stalk is used to make the semi-synthesis or synthesis y 4 ..... 1 work plan to raise the A _U, the method of the method, which will be as in the scope of application patent (i) (/), or print or The dye mixture of claim 14 is applied to the material order. 'Incorporate 1 inch. A kind of dye as in the formula (1) of the patent application scope, which is used for semi-synthesis and especially synthetic hydrophobic fiber materials, more especially for dyeing or printing of woven materials. in. None 29